Acidic esters of oxypropylated triamines



Patented May 25, 1954 ACIDIC ESTERS OF OXYPROPYLATED TRIAMINES Melvin De Groote, University City, Mo., assignor to Petrolite Corporation, a. corporation of Delaware No Drawing. Application May 14, 1951, Serial No. 226,305

10 Claims. (Cl. 260475) The present invention is a continuation-inpart of my copending applications, Serial Nos. 104,801 filed July 14, 1949, now Patent No. 2,552,528, 109,619 filed August 10, 1949, now Patent No. 2,552,531, and 107,381, filed July 28, 1949, now Patent No. 2,552,530.

The present invention is concerned with certain new chemical products, compounds, or compositions which have useful application in various arts. It includes methods or procedures for manufacturing said new chemical products, compounds or compositions, as well as the products, compounds, or compositions themselves.

Said last aforementioned co-pending application, i. e., Serial No. 107,381, describes high molal oxypropylation derivatives of monomeric polyamino compounds With the proviso that (a) the initial polyamino reactant be free from any radical having at least 8 uninterrupted carbon atoms; (b) the initial polyamino reactant have a molecular Weight of not over 1,800 and at least a plurality of reactive hydrogen atoms; the initial polyamino reactant must be water-soluble; (cl) the oxypropylation end product must be water-insoluble; (e) the oxypropylation end product be Within the molecular weight range of 2,000 to 30,000 on an average statistical basis;

step; (9 the ratio of propylene oxide per initial reactive hydrogen atom must be within the range of 7 to 70; (h) the initial polyamino reactant must represent not more than 20% by weight of assumption of complete reaction involving the propylene oxide and initial polyamino reactant; (9') the polyamino reactant must contain at least one basic nitrogen atom; and (7c) the nitrogen atoms are linked by a carbon atom chain.

Furthermore, in said aforementioned co-pending application it was pointed out that such hydroxylated materials obtained by oxypropylation could be reacted with dicarboxy acids such as diglycollic acid to yield valuable derivatives which are satisfactory also for clemulsification of petroleum emulsions, and for that matter for various other purposes.

The present invention is concerned with a fractional ester obtained from a polycarboxy acid and a polyhydroxylated material obtained by the oxypropylation of a polyamino reactant.

More specifically the present process involves the use of a demulsifying agent which is a fractional ester obtained from a polycarboxy acid and a compound derived in turn by the oxypropylation of diethylene triamine or an equivalent triamine as hereinafter specified, having five terminal hydroxyl radicals or the equivalent, i. e., labile hydrogen atoms susceptible to oxyalkylation.

The most suitable raw material is diethylenetriamine or such product treated with several moles of ethylene oxide or glycide, or a combination of the two, and particularly diethylenetriamine treated with one to five, six or seven moles of ethylene oxide. The initial triamino compound must be characterized by (at) having 3 amino nitrogen atoms and preferably all being basic; (1)) free from any radical having 8 or more carbon atoms in an uninterrupted group; (0) must be water-soluble; and (d) have a plurality of reactive hydrogen atoms, preferably at least 3 or 4.

Needless to say, the most readily available reactant, to wit, diethylenetriamine, has 5 reactive was still the same as before, to wit, 5 mols of glycide for one mole of triamine. On the other hand, if diethylenetriamine were treated with one mole of an alkylating agent so as to introany substituted diethylenetriamine as described;

(b) the use of diethylenetriamine after treatment with l to 5 moles of ethylene oxide although a modestly increased amount of ethylene oxide can be used in light of what is said hereinafter;

(c) the use of a derivative obtained from diethylenetriamine after reaction with glycide, or a mixture of ethylene oxide and glycide.

Since reaction of diethylenetriamine with propylene oxide is invariably involved and since this oxyalkylation step is substantially the same as the use of ethylene oxide or glycide, for purpose of brevity further reference simply will be made to diethylenetriamine as illustrating the procedure, regardless of what particular reactant is selected. It is not necessary to point out, of course, that the substituted diethylenetriamines,

i. e., those where an alkyl, alicyclic, aryl-alkyl, or

aryl group has been introduced can similarly be subjected to reaction with ethylene oxide, glycide, or a combination of the two.

I also want to point out it is immaterial whether the initial oxypropylation step involves hydrogen attached to oxygen or hydrogen attached to nitrogen. The essential requirement is that it be a labile or reactive hydrogen atom. Any substituent radical present must, of course, have less than 8 uninterrupted carbon atoms in a single group.

More specifically, then, the present invention is concerned with certain hydrophile synthetic products; said hydrophile synthetic products being the acidic fractional esters derived by reaction between (A) a polycarhoxy acid and (B) high molal oxypropylation derivatives of monomeric triamino compounds, with the proviso that (a) the initial triamino reactant be free from any radical having at least 8 uninterrupted carhon atoms; (b) the initial triamino reactant have a molecular weight of not over 800 and at least a plurality of reactive hydrogen atoms; (0) the initial triamino reactant must be water-soluble; (d) the oxypropylation end product must he water-insoluble and kerosene-soluble; (e) the oxypropylation end product be within the molecular weight range of 2500 to 30,000 on an average statistical basis: (f) the solubility characteristics of the oxypropylaticn end product in res ect to water and kerosene must be substantially the result of the oxypropylation step; (g) the ratio of propylene oxide per initial reactive hydrogen atom must be within the range of '7 to 70; (h) th initial triamino reactant must represent not more than 20% by weight of the oxypropylation end product on a statistical basis; the preceding provisos are based on the assumption of complete reaction involving the propylene oxide and initial triamino reactant; (7') the nitrogen atoms are linked by an ethylene chain, and with the further proviso that the ratio of (A) to (B) be one mole of (A) for each hydroxyl radical present in (B).

What has been said previously in regard to the materials herein described and particularly for use as demulsifiers with reference to fractional esters may be and probably is an over-simplification for reasons which are obvious on further examination. It is pointed out subsequently that prior to esterification the alkaline catalyst can be removed by addition of hydrochloric acid. Actually the amount of hydrochloric acid added is usually SllffiCiBllt and one can deliberately employ enough acid, not only to neutralize th alkaline catalyst but also to neutralize the amino nitrogen atom or convert it into a salt. Stated another way, a trivalent nitrogen atom is converted into a pentavalent nitrogen atom, i. e., a change involving an electrovalency indicated as follows:

wherein HX represents any strong acid or fairly strong acid such as hydrochloric acid, nitric acid, sulfuric acid, a sulphonic acid, etc., in which H represents the acidic hydrogen atom and X represents the anion. Without attempting to complicate the subsequent description further it is obvious then that one might have esters or one might convert the esters into ester salts as described. Likewise another possibility is that under certain conditions one could obtain amides. The explanation of this latter fact resides in this observation. In the case of an amide, such as acetamide, there is always a question as to whether or not oxypropylation involves both amide nitrogen atom so as to obtain a hundred per cent yield of the dihydroxylated compound. There is some evidence to at least some degree that a monohydroxylated compound is obtained under some circumstances with one amido hydrogen atom remaining without change.

Another explanation which has sometimes appeared in the oxypropylation of nitrogen-containing compounds particularly such as acetamide, is that the molecule appears to decompose under conditions of analysis and unsaturation seems to appear simultaneously. One suggestion has been that one hydroxyl is lost by dehydration and that this ultimately causes a break in the molecule in such a way that two new hydroxyls are formed. This is shown after a fashion in a highly idealized manner in the following way:

,- a speculative explanation is concerned, one need only consider the terminal radicals, as shown. Such suggestion is or interest only because it may la a possible explanation of how an increase in hydroxyl value does take place which could be interpreted as a decrease in molecular weight. This matter is considered consequently in the final paragraphs of Part 2. This same situation seems to apply in the oxypropylation of at least some polyalkylene amines and thus is of significanoe in the instant situation.

In the case of higher polyamines there is evidence that all the available hydrogen atoms are not necessarily attacked, at least under comparatively modest oxypropylation conditions,

particularly when oxypropylation proceeds at low temperature as herein described, for instance, about the boiling point of water. For instance, in the case of diethylene triamine there is some evidence that one terminal hydrogen atom only in each of the two end groups is first attacked by propylene oxide and then the hydrogen atom attached to the central nitrogen atom is attacked. It is quite possible that three long propylene oxide chains are built up before the two remaining hydrogens are attacked and perhaps not attacked at all. This, of course, depends on the conditions of oxypropylation. However, analytical procedure is not entirely satisfactory in some instances in differentiating between a reactive hydrogen atom attached to nitrogen and a reactive hydrogen atom attached to oxygen.

In the case of triethylenetetramine the same situation seems to follow. One hydrogen atom on the two terminal groups is first attacked and then the two hydrogen atoms on the two intermediate nitrogen atoms. Thus four chains tend to build up and perhaps finally, if at all, the remaining two hydrogen atoms attached to the two terminal groups are attacked. In the case of tetraethylenepentamlne the same approach seems to hold. One hydrogen atom on each of the terminal groups is attacked first, then the three hydrogen atoms attached to the three intermediate nitrogen atoms, and then finally, if at all depending on conditions of oxypropylation, the two remaining terminal hydrogen atoms are attacked.

If this is the case it is purely a matter of speculation at the moment because apparently there is no data which determines the matter com pletely under all conditions of manufacture, and one has a situation somewhat comparable to the acylation of monoethanolamine or diethanolamine, i. e., acylation can take place involving either the hydrogen atom attached to oxygen or the hydrogen atom attached to nitrogen.

As far as the herein described compounds are concerned it would be absolutely immaterial except that one would have in part a compound which might be the fractional ester and might also represent an amide in which only one carboxyl radical of a polycarboxylated reactant was involved. By and large, it is believed that the materials obtained are obviously fractional esters, for what has been said and in light of what appears hereinafter.

However, in order to present the invention in its broadest aspect it had best be re-stated as follows: It is concerned with certain. hydrophile synthetic products; said hydrophile synthetic products being a cogeneric mixture selected from the class consisting .of acidic fractional esters, acidic ester salts, and acidic amido derivatives obtained by reaction between (A) a polycarboxy acid, and (B) high molal oxypropylation derivatives of monomeric triamino compounds, with the proviso that (a) the initial triamino reactant be free from any radical having at least 8 uninterrupted carbon atoms; (b) the initial triamino reactant have a molecular weight of not over 800 and at least a plurality of reactive hydrogen atoms; (0) the initial triamino reactant must be water-soluble; (d) the oxypropylation end product must be water-insoluble, and kerosene-soluble; (e) the oxypropylation end product be within the molecular weight range of 2500 to 30,000 on an average statistical basis; (1) the solubility characteristics of the oxypropylation end product in respect to water and kerosene must be substantially the result of the oxypropylation step; (c) the ratio of propylene oxide per initial reactive hydrogen atom must be with in the range' of 7 to '70; (h)' the initial triamino reactant must represent not more than 20% by reasons which are apparent in light of A statistical basis; (2) the preceding provisos are amino reactant; the nitrogen atoms are linked by an ethylene chain, and with the final proviso that the ratio of (A) to (B) be one mole of (A) for each hydroxyl radical present in (B).

Although the herein described products have a number of industrial-applications, they are of particular value for resolving petroleum emulsions of the water-in-oil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion. This specific application is described and claimed in my co-pending application, Serial No. 226,304, filed May 14, 1951.

The new products are useful as wetting, detergent and leveling agents in the laundry, textile and dyeing industries; as wetting agents and de sewage, coal washing waste water, and various trade wastes and the like; as germicides, insecticides, emulsifying agents as, for example, for cosmetics, spray oils, water-repellent textile finishes; as lubricants, etc.

For convenience, what is said hereinafter will be divided into four parts;

Part 1 is concerned with the preparation of the oxypropylation derivatives of diethylene triamine or equivalent initial reactants;

Part 2 is concerned with the preparation of the esters from the oxypropylated derivatives;

Part 3 is concerned with the nature of the oxypropylation derivatives insofar that such cogeneric mixture is invariably obtained, and

Part 4 is concerned with certain derivatives which can be obtained from these acidic esters and which, in turn, are valuable for a wide variety of purposes.

PART 1 For a number of well known reasons equipment, whether laboratory size, semi-pilot plant size, pilot plant size, or large scale size, is not as a rule designed for a particular alkylene oxide. Invariably and inevitably, however, or particularly in the case of laboratory equipment and pilot plant size the design is such as to use any of the customarily available alkylene oxides. i. e., ethylene oxide, propylene oxide, butylene oxide, glycide, epichlorohydrin, styrene oxide, etc. In the subsequent description of the equipment it becomes obvious that it is adapted for oxyethylation as well as oxypropylation.

Oxypropylations are conducted under a wide variety of conditions, not only in regard to presence or absence of catalyst, and the kind of catalyst, but also in regard to the time of reaction, temperature of reaction, speed of reaction, pressure during reaction, etc. For instance, oxyalkylations can be conducted at temperatures up to approximately 200 C. with pressures in about the same range up to about 280 pounds per square inch. They can be conducted also at temperatures approximating the boiling pointof water or slightly above, as for example to C. Un-

der such circumstances the pressure will be less than pounds per square inch unless some special procedure is employed as is sometimes the case, to wit, keeping an atmosphere of inert gas such as nitrogen in the vessel during the reaction. Such low-temperature-low reaction rate oxypropylations have been described very completely in U. S. Patent No. 2,448,664 to H. R. Fife et al., dated September '7, 1948. Low temperature, low pressure oxypropylations are particularly desirable where the compound being subjected to oxypropylation contains one, two or three points of reaction only, such as monohydric alcohols, glycols and triols.

The initial reactants in the instant application contain at least 2 reactive hydrogens and for this reason there is possibly less advantage in using low temperature oxypropylation rather than high temperature oxypropylation. However, the reactions do not go too slowly and this particular procedure was used in the subsequent examples.

Since low pressure-low temperature low-reaction-speed oxypropylationsrequire considerable time, for instance, 1 to I days of 24 hours each to complete the reaction they are conducted as a rule whether on a laboratory scale, pilot plant scale, or large scale, so as to operate automatically. The prior figure of seven days applies especially to large-scale operations. I have used, conventional equipment with two added automatic features: (a) a solenoid controlled valve which shuts off the propylene oxide in event that the temperature gets outside a predetermined and set range, for instance, 95 to 120 C., and (b) another solenoid valve which shuts ofi" the propylene oxide (or for that matter ethylene oxide if it is being used) if the pressure gets beyond a predetermined range, such as 25 to pounds. Otherwise, the equipment is substantially the same as is commonly employed for this purpose where the pressure of reaction is higher, speed of reaction is higher, and time of reaction is much shorter. In such instances such automatic controls are not necessarily used.

Thus, in preparing the various examples I have found it particularly advantageous to use laboratory equipment or pilot plant which is designed to permit continuous oxya-lkylation whether it be oxypropylation or oxyethylation.

With certain obvious changes the equipment can I be used also to permit oxyalkylation involving the use of glycide where no pressure is involved except the vapor pressure of a solvent, if any, which may have been used as a diluent.

As previously pointed out the method of using propylene oxide is the same as ethylene oxide. This point is emphasized only for the reason that the apparatus is so designed and constructed as to use either oxide.

} The oxypropylation procedure employed in the preparation of the oxyalkylated derivatives has been uniformly the same, particularly in light of the fact that a continuous automatically-controlled procedure was employed. In this procedure the autoclave was a conventional autoclave made of stainless steel and having a capacity of approximately 15 gallons and a working pressure of one thousand. pounds gauge pressure. This pressure obviously is far beyond any requirement as far as propylene oxide goes unless there is a reaction of explosive violence involved due to accident. The autoclave was equipped with the conventional devices and openings, such as the variable-speed stirrer operating at speeds from R. P; M. to 500 R. P. M.: thermometer well and thermocouple for mechanical thermometer; emptying outlet; pressure gauge, manual vent line; charge hole for initial reactants; at least one connection for introducing the alkylene oxide, such as propylene oxide or ethylene oxide, to the bottom of the autoclave; along with suitable devices for both cooling and heating the autoclave, such as a cooling jacket, and, preferably, coils in addition thereto, with the jacket so arranged that it is suitable for heating with steam or cooling with water and further equipped with electrical heating devices. Such autoclaves are, of course, in essence small-scale replicas of the usual conventional autoclave used in oxyallrylation procedures. In some instances in exploratory preparations an autoclave having a smaller capacity. for instance, approximately 3 /2 liters in one case and about 1% gallons in another case, was used.

Continuous operation, or substantially continuous operation, was achieved by the use of a separate container to hold the alkylene oxide being employed, particularly propylene oxide. In conjunction with the smaller autoclaves, the container consists essentially of a laboratory bomb having a capacity of about one-half gallon, or somewhat in excess thereof. In some instances a larger bomb was used, to wit, one having a capacity of about one-gallon. This bomb was equipped, also, with an inlet for charging, and an eductor tube going to the bottom of the container so as to permit discharging of alkylene oxide in the liquid phase to the autoclave. A bomb having a capacity of about pounds was used in connection with the 15-gallon autoclave. Other conventional equipment consists, of course, of the rupture disc, pressure gauge, sight feed glass, thermometer connection for nitrogen for pressuring bomb, etc. The bomb was placed on a scale during use. The connections between the bomb and the autoclave were flexible stainless steel hose or tubing so that continuous weighings could be made without breaking or making any connections. This applies also to the nitrogen line, which was used to pressure the bomb reservoir. To the extent that it was required, any other usual conventional procedure or addition which provided greater safety was used, of course, such as safety glass protective screens, etc.

Attention is directed again to what has been said previously in regard to automatic controls which shut off the propylene oxide in event tem perature of reaction passes out of the predetermined range or if pressure in the autoclave passes out of predetermined range.

With this particular arrangement practically all oxypropylations become uniform in that the reaction temperature was held within a few degrees of any selected point, for instance, if C. was selected as the operating temperature the maximum point would be at the most C. or 112 C., and the lower point would be 95 or possibly 98 C. Similarly, the pressure was held at approximately 30 pounds within a 5-pound variation one way or the other, but might drop to practically zero, especially where no solvent such as xylene is employed. The speed of reaction was comparatively slow under such conditions as compared with oxyalkylations at 200 C. Numerous reactions were conducted in which the time varied from one day (24 hours) up to three days (72 hours) for completion of the final member of a series. In some instances the reaction may take place in considerably less time, i. e., 24 hours or less, as faras a partial oxypropylation is concerned. The minimum time recorded was about a 6-hour period in a single step. Reactions indicated as being complete in 7 or 8 hours may have been complete in a lesser period of time in light of the automatic equipment employed. In the addition of propylene oxide, in the autoclave equipment as far as possible the valves were set so all the propylene oxide if fed continuously would be added at a rate so that the predetermined amount would react within the first hours of the 8-hour period or two-thirds of any shorter period. This meant that if the reaction was interrupted automatically for a period of time for pressure to drop or temperature to drop the predetermined amount of oxide would still be added in most instances well within the prede termined time period. Sometimes where the addition was a comparatively small amount in an the example and using 4.

When operating at a perature, for instance, an unreacted alkylene oxide such as propylene is, of course, an inherent danger and appropriate steps must be taken to safeguard against this possibility; if need be a sample must be with- However, as has been pointed out previously, operating at a low pressure and a low temperature even in large scale operations as much as a week or ten days time may lapse to In a number of operations the counterbalance scale or dial scale reaction the scale crating device use on larger equipment than laboratory size autoclaves, to wit, on semi-pilot plant or pilot plant size, as well as on large scale size. This final stirring period is intended to avoid the presence of unreacted oxide.

In this sort of operation, of course, the temperature range was controlled automatically by either use of cooling water, steam, or electrical 10 heat, so as to raise or lower the temperature. The pressuring of the propylene oxide into the reaction vessel was were conventional including the gauges, check valves and entire equipment. As far as I am aware at least two firms, and possibly three, specialize in autoclave equipment such as I have employed in the laboratory, and are prepared to furnish equipment of this same kind. Similarly pilot plant equipment is available. This point is simply made as a precaution in the direction of safety. Uxyalkylations, particularly involving ethylene oxide, glycide, propylene oxide, etc., should not be conducted except in equipment specially designed for the purpose.

It is to be noted in the present instance one may or may not have basic nitrogen atoms present. For example, if a phenyl radical is attached trogen atoms and thus the addition of an alkaline catalyst can be elminated in the early stages of oxypropylation or oxyethylation. This is illustrated subsequently by the fact that oxypropylation was permitted to go through the first stage without the addition of alkaline catalyst.

Ezcample 1a Th particular autoclave employed was one with a capacity of approximately 15 gallons or on the average of about pounds of reaction The speed of the stirrer could be varied from to 350 R. P. M. The initial charge was 13.25 pounds diethylenetriamine. Even though this reagent itself is alkalin 1.25 pounds of caustic soda were added. The reaction pot was flushed out with nitrogen, the autoclave sealed, and the automatic devices adjusted for injecting 85 pounds of propylene oxide in a 9-hour period. The pressure regulator was set for a, maximum sure. This comparatively low pressure was the result of the fact that the reactant per se was basic and also because considerable catalyst was added. The propylene oxide was added rather slowly at the rate of about 11 pound per hour and, more important, the selected temperature was within the range of 220-225 F. (somewhat higher than the boiling point of water). The ini- Ezrample 2a 54.75 pounds of reaction mass identified as Example la, preceding, and equivalent to 7.30 parts and pressure as in Example 112, preceding. The

time period was shorter, to wit, 5 hours. The

11 oxide was added at the rate of about 10 pounds per hour. At the end of the reaction period part of the sample was withdrawn and subjected to further oxypropylation as described in Example 3a, following.

Example 3:1

52.63 pounds of the reaction mass identified as Example 2a, preceding, equivalent to 3.91 pounds of polyamine, 48.35 pounds of propylene oxide, and .37 pound of caustic soda, were subjected to further oxypropylation in the same manner described in the two preceding examples. The amount of propylene oxide added was 43.5 pounds. The conditions of reaction were the same as in the preceding example and the time period was approximately the same, to wit, 6 hours. Th addition of the oxide was at a somewhat slower rate, being about 8 pounds per hour. When the reaction was complete part of th sample was withdrawn and the remainder subjected to further oxypropylation as described in Example 4a, immediately following.

Example 4a riod Was 7 hours and the addition rate was at the rate of approximately 6 pounds per hour.

EICCVIMJZG 5a In order to illustrate the effect of first adding a plurality or ethylene oxide per mole of polyamine, for instance, about 6 or 7 moles of oxide per mole of amine, a new series was prepared which illustrated additionally the efiect of increased theoretical molecular weight. In this instance, of course, th ethylene oxide was added first.

13.75 pounds of diethylenetriamine were reacted first with 35.5 pounds of ethylene oxide and then with 36.25 pounds of propylene oxide. No catalyst was added since the reactant was decidedly basic. as previously pointed out. The temperature. employed. was substantially higher than in the. previous examples, to. wit, 250-255 F. The maximum pressure was 3537 pounds per square inch. What has been said in regard to pressure in Example 1a applies also in this particular example and in all subsequent examples, that is, Examples 5a through 10a, inclusive. Similarly, the temperature employed, to wit, 250- 255 F1, applies in all subsequent examples, Nos. 5a through 10a, inclusive, therefore, no further reference will be made to either temperature or pressure. In each instance the reaction was not started until the automatic devices had raised the temperature of the reaction mass to approximately- 240 -250 F. The first reaction required approximately 9 hours. Both oxides were added at the rate of about 10 pounds per hour. In all respects the. reaction was conducted with the same apparatus and in the same manner as in Example 1a, preceding. At the completion of the reaction part of the reaction mass was withdrawn and the remainder subjected to further oxypropylation as noted in Example 6a, immediately following.

Example 6a 35.75 pounds of the reaction mass identified as Example 5a, preceding, and equivalent to 5.76 pounds of the polyamine, 14.82 pounds of ethylene oxide, and 15.17 pounds of propylene oxide were subjected to oxypropylation with 43.75 pounds of propylene oxide. In this instance .75 pound of caustic soda was added as a catalyist. The time period employed was 2 hours. The propylene oxide was added at the rate of somewhat better than 20 pounds per hour. At the completion of the reaction, part of the reaction mass was withdrawn as a sample and the remainder was subjected to further oxypropylation as described in Example 7a, immediately following.

Example 7 a 43.13 pounds of the reaction mass identified as Example 6a, preceding, and equivalent to 3.10 pounds of the polyamine, 7.95 pounds of ethylene oxide, 31.68 pounds of propylene oxide and .40 pound of caustic soda, were subjected to reaction, without adding any more catalyst, with 20.25 pounds of propylene oxide. The time involved was 3 hours. The addition rate was at about 8 pounds per hour. At the end of the reaction part of the mass was withdrawn as a sample and the remainder subjected to further oxypropylation as described in Example 8a, following.

Example 8a 11 pounds of the reaction mass identified as Example 7a, immediately preceding, and equivalent to 1.98 pounds of polyamine, 5.21 pounds of ethylene oxide, 33.55 pounds of propylene oxide and .26 pound of caustic soda, were subjected to reaction with 23.75 pounds of propylene oxide. No. catalyst was introduced. The time period was 5 hours. The rate of addition of oxide was about 6 pounds per hour. At the end of the reaction period part of the reaction mass was withdrawn and the remainder subjected to further oxypropylation as described in Example 9a, immediately following.

. Example 9a 44.37 pounds of the reaction mass identified as Example 8a, preceding, and equivalent to 1.36 pounds of the polyamine, 3.58 pounds of ethylene oxide, 39.25 pounds of propylene oxide, and .18 pound of caustic soda were subjected to reaction with 37.75 pounds of propylene oxide without adding any more catalyst. The time required was 6 hours. The rate of addition was about 6 pounds per hour. At the end of the reaction period part of the sample was withdrawn and the remainder subjected to a final oxypropylation in the manner described in Example 10a, immediately following.

Example 10a 56.63 pounds of the reaction mass identified as Example 9a, preceding, were subjected to further reaction with 16.25 pounds of propylene oxide and without adding any more catalyst. The time required to add the oxide was 5 hours. The rate of addition was about 4 pounds per hour.

What has been said herein is presented in tabular form in Table I immediately following with some added information as to molecular weight and as to solubility of the reaction product in water, xylene, and kerosene.

TABLE 1 Composition Before Composition at End Ml.J W. M

M y ax Hyd. T133 Pres 'Ilme Theo Amine Oxide Cata- De- OFD lbs. (hrs) Mol Amt, Amt, lyst, tersq. Wt lbs. lbs. lbs. min. in.

it indicates ethylene The ox1de w1th E after oxide; and the oxide propylene oxide.

Examples 10 and 2a were soluble in water, soluble in xylene, and insoluble in kerosene; Example 3a was emulsifiable in water, soluble in xylene, and dispersible in kerosene; Example 4a was insoluble in water, and soluble in both xylene and kerosene.

Examples 5a and 6a were soluble in water, soluble in xylene but insoluble in kerosene; Example 100. were insoluble in water, soluble in xylene, and dispersible, dispersible to insoluble,and soluble in kerosene, respectively.

Referring to the first series of compounds, Examples 1a through 4a, in a similar series I have prepared compounds in which theoretical molecular weights have ranged as high as 8,000 to 10,000, with hydroxyl molecular weights running from 3000 to 3,600. In these instances the products prior to esterification were water-insoluble, xylene-soluble and kerosene-soluble.

The final product, i. e., at the end of the oxypropylation step, was apt to be either a faint straw color, or sometimes it would have a more definite dark amber or amber-reddish tinge. In the later stages the product was invariably water-insoluble anad kerosene-soluble. This is characteristic of all the products obtained from the triamine products herein described. Needless to say if more ethylene oxide radicals were introduced into the initial raw material the initial product is more water-soluble and one must go to higher molecular weights to produce waterinsolubility and kerosene-solubility, for instance, molecular weights such as 10,000 to 12,000 or more on a theoretical basis, and 6,000 to 8,000 or 10,000 on a hydroxyl molecular weight basis. If, however, the initial triamine compound is treated with one or more or perhaps several moles of butylene oxide then the reverse effect is obtained and it takes less propylene oxide to produce water-insolubility and kerosene-solubility. These products were, of course, slightly alkaline due in part to the residual caustic soda employed. This would also be the case if sodium methylate were used as a catalyst.

Speaking of insolubility in water or solubility in kerosene such solubility test can be made simply by shaking small amounts of the materials in a test tube with water, for instance, using 1% to 5% approximately based on the amount of water present.

Needless to say, there is no complete conversion of propylene oxide into the desired hydroxylated compounds. This is indicated by the fact with P after it indicates 20 on basis of Actually, there is no completely satisfactory method for determining molecular weights of these types of compounds is illustrated by some of the examples appearing in the patent previously mentioned.

PART 2 As previously pointed out the present invention is concerned with acidic esters obtained from the oxypropylated derivatives described in Part- 1, immediately preceding, and polycarboxy acids, particularly tricarboxy acids like citric and dicarboxy acids such as acids, or unsaturated monocarboxy acids having Reference to the acid-in the claims obviously includes the involving the esteriflcation of triethanolamine. Possibly the addition of an acid such as hydrochloric acid if employed for elimination of the basic catalyst also combines with the basic nitrogen present to form a salt. In any event, however, such procedure does not effect conventional esteriflcation procedure as described herein.

Needless to say, various compounds may be used such as the low molal ester, the anhydride, the acyl chloride, etc. However, for purpose of economy it is customary to use either the acid or the anhydride. A conventional procedure is employed. On a laboratory scale one can employ a resin pot of the kind described in U. S. Patent No. 2,499,370, dated March I, 1950, to DeGroote & Keiser, and particularly with one more open ing to permit the use of a porous spreader if hydrochloric acid gas is to be used as a catalyst. Such device or absorption spreader consists of minute alundum thimbles which are connected to a glass tube. One can add a sulfonic acid such as paratoluene sulfonic acid as a catalyst. There is some objection to this because in some instances there is some evidence that this acid catalyst tends to decompose or rearrange heat-oxypropylated compounds, and particularly likely to do so if the esterification temperature is too high. In the case of polycarboxy acid such as diglycollic acid, which is strongly acidic there is no need to add any catalyst. acid gas has one advantage over paratoluene sulfonic acid and that is that at the end of the reaction it can be removed by flushing out with nitrogen, whereas there is no reasonably convenient means available of removing the paratoluene sul fonic acid or other sulfonic acid employed. If hydrochloric acid is employed one need only pass the gas through at an exceedingly slow rate so as to keep the reaction mass acidic. Only a trace of acid need be present. I have employed hydrochloric acid gas or the aqueous acid itself to eliminate the initial basic material. My preference, however, is to use no catalyst whatsoever.

The products obtained in Part 1 preceding may contain a basic catalyst. As a general procedure I have added an amount of half-concentrated hydrochloric acid considerably in excess of what is required to neutralize the residual catalyst. The mixture is shaken thoroughly and allowed to stand overnight. It is then filtered and refluxed with the xylene present until the water can be separated in a phase-separating trap. As soon as the product is substantially free from water the distillation stops. This preliminary step can be carried out in the flask to be used for esterifieation. If there is any further deposition of sodium chloride during the reflux stage needless to say a second filtration may be required. In any event the neutral or slightly acidic solution of the oxypropylated derivatives described in Part 1 is then diluted further with sufficient xylene, decalin, petroleum solvent, or the like, so that one has obtained approximately a 40% solution. To this solution there is added a polycarboxylated reactant as previously described, such as phthalic anhydride, succinic acid or anhydride, diglycollic acid, etc. The mixture is refluxed until esteriflcation is complete as indicated by elimination of water or drop in carboxyl value. Needless to say, if one produces a half-ester from an anhydride such as phthalic anhydride, no water is eliminated. However, if it is obtained from diglycollic acid, for example, water is eliminated. All such procedures are conventional and havebeen so The use of hydrochloric r matic in character.

thoroughly described in the literature that further consideration will be limited to a few examples and a comprehensive table.

Other procedures for eliminating the basic residual catalyst, if any, can be employed. For example, the oxyalkylation can be conducted in absence of a solvent or the solvent removed after oxypropylation. Such oxypropylation end product can then be acidified with just enough concentrated hydrochloric acid or just neutralize the residual basic catalyst. To this product one can then add a small amount of anhydrous sodium sulfate (sufficient in quantity to take up any water that is present) and then subject the mass to centrifugal force so as to eliminate the hydrated sodium sulfate and probably the sodium chloride formed. The clear, somewhat viscous straw-colored to amber liquid so obtained may contain a small amount of sodium sulfate or sodium chloride but, in any event, is perfectly acceptable for esteriflcation in the manner described.

It is to be pointed out that the products here described are not polyesters in the sense that there is a plurality of both triamino radicals and acid radicals; the product is characterized by having only one triamino radical.

In some instances and, in fact, in many instances I have found that in spite of the dehydration methods employed above that a mere trace of water still comes through and that this mere trace of water certainly interferes with the acetyl or hydroxyl value determination, at least when a number of conventional procedures are used and may retard esterification, particularly where there is no sulfonic acid or hydrochloric acid present as a catalyst. Therefore, I have preferred to use the following procedure: I have employed about 200 grams of the polyhydroxylated compound as described in Part 1, preceding; 1 have added about 60 grams of benzene, and then refluxed this mixture in the glass resin pot using a phase-separating trap until the benzene carried out all the water present as water of solution or the equivalent. Ordinarily this refluxing temperature is apt to be in the neighborhood of 130 to possibly 150 C. When all this water or moisture has been removed I also withdraw approximately grams or a little less benzene and then add the required amount of the carboxy reactant and also about 150 grams of a high boiling aromatic petroleum solvent. These solvents are sold by various oil reflneri'es and, as far as solvent effect act as if they were almost completely aro- Iypical distillation data in the particular type I have employed and found very satisfactory is the following:

I.'.B.P., 142 C. m1., 242 C. 5 m1., 200 C. m1., 244 C. 10 m1., 209 C. m1., 248 C. 15 m1., 215 C. m1., 252 C. 20 m1., 216 C. m1., 252 C. 25 m1., 220 C. m1., 260 C. 30 m1., 225 C. m1., 264 C. 35 m1., 230 C. m1., 270 C. 40 m1., 234 C. m1., 280 C. 45 m1., 237 C. m1., 307 C.

After this material is added, refluxing is continued and, of course, is at a higher temperature, to wit, about to C. If the carboxy reactant is an anhydride needless to say no water of reaction appears; if the carboxy reactant is an acid, water of reaction should appear and should be eliminated at the above reaction temperature.

17 If it is not eliminated I simply separate out another or cc. of benzene by means of the phase-separating trap and thus raise the temperature to 180 or 190 C., or even to 200 C., if need be. My preference is not to go above 200 C.

The use of such solvent is extremely satisfactory provided one does not attempt to remove the solvent subsequently except by vacuum distillation and provided there is no objection to a little residue. Actually, used for a purpose such as demulsification the solvent might just as well be allowed to remain. If the solvent is to be removed by distillation, and particularly vacuum distillation, then the high boiling aromatic petroleum solvent might well be replaced by some more expensive solvent, such as decalin or an alkylated decalin which has a rather definite or close range boiling point. The removal of the solvent, of course, is purely a conventional procedure and requires no elaboration.

In a number of the examples the #7-3 solvent was entirely satisfactory, as, for example, in Examples 71) through 250. This is particularly the case when the oxypropylated derivative showed decreased water-solubility. However, when the product showed significant Water-solubility the diificulty arose that at the end of the esterifica- Ex. N0. Theo.

"551 29 g ag TOXy .0

Ester Cmpd. 11.0.

5 #7-3. Afterwards when these materials are 10 tion reaction the solvent and resultant, or reaction mass, is not homogeneous. Thus, in Examples 1b through approximately two-thirds of the solvent indicated was first added as solvent about 15% of the solvent was added as methanol and another 15% as diethyleneglycol diethylether. These solvent properties can be varied somewhat Without any change,.the object being merely to eliminate the Water in presence of water-insoluble solvents and then add suitable semi-polar compounds to give a homogeneous solution. Other obvious solvents would serve. In the case of Examples 26b through 615, xylene was used to the extent of about two-thirds the solvent indicated and when all the water was eliminated approximately 35% of methanol was added. In this instance a homogeneous solution was obtained. Here, again, any suitable variant could be employed.

Another obvious procedure, of course, is merely to distill 011 a solvent such as xylene or solvent #7-3 and then dissolve the product in a semipolar solvent, such as methanol, ethanol, propanol, etc. It is purely a matter of convenience to first employ a non-polar solvent (Water-insoluble) to eliminate the water during distillation and then add a suitable polar solvent (hydrophile) to give a single-phase system.

TABLE 2 5 M01. Actual Wt. Amt. of Hy- Based Hyd P013" droxyl drox I on d Polycarboxy Rcactant carboxy Value g; Actual (grs Reaetant of H. O. H V (grs) 222 250 672 196 Diglycolic Acid 39. 0 222 250 672 195 Oxalic Acid 36. 5 222 250 672 210 Malcic Anhydridm 30. 6 222 250 672 193 Phthalic Anhyd 42. 5 222 250 672 194 Citraconic Anhyd 23. 2 222 250 672 211 Aconitic Acid 54. 5 163 189 1, 188 191 Diglycolic Acid 26.8 163 189 l, 188 202 Oxalic Acid 26. 6 163 189 1,188. 203 Maleic Anhydride 20. 8 163 189 1,188 205 Phthalic Anhyd 31. 6 163 189 1, 188 210 Aconitic Acid" 38, 2 163 189 1,188 202 Oitraconic Anhyd 23. 6 89 123 1, 820 207 iglycolic Acid 53. 4 89 123 1, 820 207 Oxalic Acid... 7 50.0 89 123 1,820 208 Maleic Anhydride 39.2 89 123 1,820 205 Phthalic Anhydrid 58.4 89 123 1,820 210 Aconitic Acid. 70.0 89 123 l, 820 203 Citraconic AnhytL 44.3 89 123 1,820 199 lvlaleic Anhydride 37. 4 54. 5 84 2, 668 213 Diglycolic Acid 42. 8 54. 5 84 2, 668 204 Oxalic Acid 38, 6 54. 5 84 2, 668 200 Maleic Anhydride 29. 4 54. 5 84 2, 668 213 Phthalic Anhyd. 47. 3 54. 5 84 2, 668 204 Aconitic Acid. 53. 3 54. 5 84 2. 668 200 Citraconic Anhy 33. 6 262 312 540 191 Diglvcolic Acid 142 262 312 540 i 191 Oxalic Acid 133. 7 262 312 540 191 aleic Anhy 104 262 312 540 191 Phthalic Anhy 157 262 312 540 191 Citraconic Anhyd 118.8 262 312 V 540 190 Aconitic Acid 183 120 189 912 197 Diglycolic A0 86. 8 120 189 912 197 xalic Acid 81. 6 120 189 912 197 Mnlcic Anhydride. 63. 5 120 189 912 197 Phthalic Anhydridc.- 95. 9 120 189 912 197 Citraconic Anhyd 72. 57 120 189 912 197 Aconitic AcicL- 112. 80. 5 144. 5 1,164 201 Diglycolic Acid. 69. 38 80. 5 144. 5 1, 164 201 I Qxalic Acid" 65. 24 80. 5 144. 5 1, 164 201 Maleic Anhydri 50. 74 80. 5 144. 5 l, 164 201 Phthalic Anhydride... 76. 6 80. 5 144. 5 1, 164 201' 'Oitraccnic Anhyd. 57. 9 80.5 144. 5 1,164 201 Aconitic Acid 90.1 50. 3 97. 5 1, 725 204 Dielycolic Acid 47. 5 50.3 97.5 1.725 204 Oxalic Acid 44. 68 50.3 97. 5 1,725 204 Malcic Anhydrid 33. 75 50. 3 97. 5 1.725 204 Phthalic Anhydride... 52. 4 50. 3 97. 5 1, 725 204 Oitraconic Anhyd... 39. 7 50. 3 97.5 1, 725 204 'Aconitic Acid 61. 7 27. 2 63. 4 2, 655 206 Diglycolic Acid 30. 35 27.2 63. 4 2, 655 206 Oxalic Acid 28. 5 27. 2 63. 4 2, 655 206 lvlaleic Anhydride- 22. 2 27. 2 63. 4 2, 655 206 Phthalic Anhydridc.-. 34. 0 27. 2 63.4 2, 655 206 Citraconic Anhyd 25. 8 27. 2 63. 4 2,655 .200 Aconitic Acid. 40. 1 21. 1 56. l 3. 000 207 Diglycolic Acid. 27. 7 21. l 56. 1 3, 000 207. Oxalic Acid- 26. 1 21. 1 56. 1 3, 000' 207 Maleic Anhydride- 20. 29 21. 1 56. 1 3, 000 207 Phthalic Anhydride... 30. 64 21. l 56. l 3, 000 207 Citraconic Anhyd 23. 05 2]. 1 56. 1 3, 000 207 Aconitic Acid 35. 8

TABLE 3 Maximum Ex. No. Amt. Sol- Time of of Acid Solvent vent gfffi g Esterifiw; Ester (era) a F. tion (hrs) #7-3, methanol dlethyl cagbitol' for manufacturing the esters If The procedure has been illustrated by preceding examples. for any reason reaction does not take place in a manner that is acceptable, attention. should be directed to the following details: (a) Recheck the hydroxyl or acetyl value of the oxypropylated derivative and use a stoichiometrically equivalent amount of acid; (b) If the r'e action does not proceed with reasonable speed either raise the temperature indicated or else extend the period of time up to, 12 or 16 hours if need be; (c) It necessary, use /2% of p toluene sulfonic acid or some other acid as a catalyst provided that the hydroxylated compound is not basic; (d) If the esterification does not produce a clear product a check should be made to see if an inorganic salt such as sodium chloride or sodium sulfate is not precipitating out. Such salt should be eliminated, at least for exploration experimentation, and can be removed by filtering. Everything else being equal as the size of the. molecule increases and the reactive hydroxyl radical represents a smaller fraction of the entire molecule, more difliculty is involved in obtaining complete esterification.

OOMPBr E Water Out (cc) -12. b. {solidified Discarded.

chews-coo XXRKX Even under the mo tively low temperatur positions is still obscure. products can contribute a substantial prop of the final cogeneric reaction mixture.

ous suggestions have of these compounds, such as b (0- with the appearance i. e., of an aldehyde, ketone, or some instances an a metric amount of a polycarb oxypropylated derivative results in an exces the carboxylated rea 70 cated by the hydroxyl value.

boxylic reactant,

ratio of carboxylic reactant.

st carefully controlled conditions of oxypropylation involving comparae and long time of reaction there are formed certain compounds whose com- Such side reaction ortion Varibeen made as to the nature eing cyclic polymers of propylene oxide, dehydration products of a vinyl radical, or isomers of propylene oxide or derivatives thereof, allyl alcohol. In ttempt to react the stoichiooxy acid with the ctant for the reason that apparently under conditions of reaction less reactive hydroxyl radicals are present then indi- Under such clr cumstances there is simply a residue of the carwhich can be removed by filtration or, if desired, the esterification procedure can be repeated using an appropriately reduced iations as appear Even the determination of the hydroxyl value and conventional procedure leaves much to be desired due either to the cogeneric materials previously referred to, or for that matter, the presence of any inorganic salts or propylene oxide. Obviously this oxide should be eliminated.

The solvent employed, if any, can be removed from the finished ester by distillation and particularly vacuum distillation. The final products or liquids are generaly pale amber to dark amber in color, and show moderate viscosity. They can be bleached with bleaching clays, filtering chars, and the like. However, for the purpose of demulsification or the like color is not a factor and decolorization is not justified.

In the above instance I have permitted the solvents to remain present in the final reaction mass. In other instances I have followed the same procedure using decalin or a mixture of decalin or benzene in the same manner and ultimately removed all the solvents by vacuum distillation. Appearances of the final products are much the same as the polyols before esterification and in some instances were somewhat darker in color and had a reddish cast and per haps were somewhat more viscous.

PART 3 In the hereto appended claims the demulsifying agent is described as an ester obtained from a polyhydroxylated material prepared from a triamine. If one were concerned with a monohydroxylated material or a dihydroxylated material one might be able to write a formula which in essence would represent the particular prod not. However, in a more highly hydroxylated material the problem becomes increasingly more difficult for reasons which have already been which can be examined by merely considering for the moment a monohydroxylated material.

Oxypropylation involves the same sort of varin preparing high molal polypropylene glycols. Propylene glycol has a secondary alcoholic radical and a primary alcohol radical. Obviously then polypropylene glycols could be obtained, at least theoretically, in which two secondary alcoholic groups are united or a secondary alcohol group is united to a primary alcohol group, etherization being involved, of course, in each instance. Needless to say, the same situation applies when one has oxypropylated pclyhydric materials having 4 or more hydroxyls, or the obvious equivalent.

Usually no effort is made to differentiate between oxypropylation taking place, for example, at the primary alcohol radical or the secondary alcohol radical. Actually, when such products are obtained, such a high molal polypropylene glycol or the products obtained in the manner herein described one does not obtain a single derivative such as HO(RO)nH or (RO)1LH in which n has one and only one value, for instance, 14, 15 or 16, or the like. Rather, one obtains a cogeneric mixture of closely related or touching homologues. These materials invariably have high molecular weights and cannot be separated from one another by any known procedure without decomposition. The properties of such mixture represent the contribution of the variour; individual members of the mixture. On a statistical basis, of course, 12 can be appropriately specified. For practical purposes one need only consider the oxypropylation of a monohy- 22 dric alcohol because in essence this is substantially the mechanism involved. Even in such instances where one is concerned with a monohydric reactant one cannot draw a single forthat by following such procedure one can readily obtain or or of such compound. However, in the case of at least be prepared as components and are manufactured conventioncomparatively large, for instance, 10, 20, 30, 40 or 50 units. If such compound is subjected to xyethylation so as to introduce 30 units of ethylene oxide, it is well known that one does not obtain a single constituent which, for the sake of convenience, may be indicated as R0 (C2H40) soOI-I Instead, one obtains a cogeneric mixture of closely related homologues, in which the formula may be shown as the following, RO'(C2H40) 11H, wherein n, as far as the statistical average goes, is 30, but the individual members present in significant amount may vary from instances where n has a value of 25, and perhaps less, to a point where 11. may represent 35 or more. Such mixture is, as stated, a cogeneric closely related series of touching homologous compounds.

Attention is directed to the article entitled Fundamental Principles of Condensation Polymerization, by Flory, which appeared in Chemical Reviews, volume 39, No. 1, page 137.

Unfortunately, as has been pointed out by Flory and other investigators, there is no satisfactory method, based on either experimental or mathematical examination, or" indicating the exact prodensation products of the kind described. This means that from the practical standpoint, i. e., the ability to describe how to make the product under consideration and how to repeat such protime without difficulty, it is to some other method of the value of n, in

duction time after necessary to resort description, or else consider formulas such as those which have appeared pr viously and which appear in the claims, as representing both individual constituents in which n has a single definite value, and also with the understanding that n represents the average statistical value based on the assumption of completeness of reaction.

This may be illustrated as follows: Assume that in any particular example the molal ratio of propylene oxide per hydroxyl is 15 to 1. In a generic formula 15 to 1 could be 10, 20 or some other amount and indicated by 12. Referring to this specific case actually one obtains products in which n probably varies from to 20, perhaps even further. The average value, however, is 15, assuming, as previously stated, that the reaction is complete. The product described by the formula is best described also in terms of method of manufacture.

The significant fact in regard to the oxypropylated polyamines herein described is that in the initial stage they are substantially all water-insoluble, for instance, up to a molecular weight of 2,500 or thereabouts. Actually, such molecular weight represents a mixture of some higher molecular weight materials and some lower molecular weight materials. The higher ones are probably water-insoluble. The product may tend to emulsify or disperse somewhat because some of the constituents, being a cogeneric mixture, are water-soluble but the bull: are insoluble. Thus one gets emulsifiability or dispersibility as noted. Such products are invariably xylene-soluble regardless of whether the original reactants were or not. Reference is made to what has been said previously in regard to kerosene-solubility. For example, when the theoretical molecular weight gets somewhere past 4,000 or at approximately 5,000 the product is kerosene-soluble and waterinsoluble. These kerosene-soluble oxyalkylation products are most desirable for preparing the esters. I have prepared hydroxylated compounds not only up to the theoretical molecular weight shown previously, 1. e., about 8,000 but some which were much higher. I have prepared them, not only from diethylenetriamine, but also from oxyethylated or oxybutylated derivatives previously referred to. The exact composition is open to question for reasons which are common to all oxyalkylations. It is interesting to note, however, that the molecular weights based on hydroxyl determinations at this point were considerably less, in the neighborhood of a third or a fourth of the value at maximum point. Referring again to previous data it is to be noted, however, that over the range shown of kerosene-solubility the hydroxyl molecular weight has invariably stayed at two-thirds or five-eighths of the theoretical molecular weight.

It becomes obvious when carboxylic esters are prepared from such high molecular weight materials that the ultimate esterification product 7 again must be a cogeneric mixture. Likewise, it is obvious that the contribution to the total molecular weight made by the polycarboxy acid is small. By the same token one would expect the effectiveness of the demulsifier to be comparable to the unesterified hydroxylated material. Remarkably enough, in many instances the prodnot is distinctly better.

PART 4 As pointed out previously the final product obtained is a fractional ester having free carboxyl radicals. Such product can be used as an intermediate for conversion into other derivatives which are effective for various purposes, such as the breaking of petroleum emulsions of the kind herein described. For instance, such product can be neutralized with an amine so as to increase its water-solubility such as triethanolamine, tripropanolamine, oxyethylated triethanolamine,

etc. Similarly, such product can be neutralized with some amine which tends to reduce the water-solubility such as cyclohexylamine, benzylamine, decylamine, tetradecylamine, octadecylamine, etc. Furthermore, the residual carboxyl radicals can be esterified with alcohols, such as low molal alcohols, methyl, ethyl, propyl, butyl, etc., and also high molal alcohols, such as octyl, decyl, cyclohexanol, benzyl alcohol, octadecyl alcohol, etc. Such products are also valuable for a variety of purposes due to their modified solubility. This is particularly true where surfaceactive materials are of value and especially in demulsification of water-in-oil emulsions.

Having thus described my invention, what I claim as new and desire to obtain by Letters Patent, is:

l. A hydrophile synthetic product which is the ester or" (A) a polycarboxy acid selected from the group consisting of acyclic and isocyclic clicarboxy and tricarboxy acids, composed of carbon, hydrogen and oxygen and having not more than 8 carbon atoms and (B) a high molal oxypropylated monomeric acyclic triamino compound, with the proviso that the monomeric triamino compound be free from any radical having at least 8 uninterrupted carbon atoms and be composed of elements selected from the group consisting of carbon, hydrogen, oxygen and nitrogen, that it have a molecular weight of not over 800 and at least a plurality of reactive hydrogen atoms, that the oxypropylated monomeric triamino compound be within the molecular weight range of 2,500 to 30,000 on an average statistical basis, that the ratio of propylene oxide per reactive hydrogen atom of the monomeric triamino compound be within the range of 7 to '70, that the monomeric triamino compound not represent more than 20% by weight of the oxypropylated monomeric triamino compound on a statistical basis, that the preceding provisos are based on the assumption of complete reaction involving the propylene oxide and the monomeric triamino compound, that the nitrogen atoms be linked by ethylene groups, and that the ratio of (A) to (B) be one mole of (A) for each reactive hydrogen atom present in (B).

2. The product of claim 1 wherein the monomeric triamino compound has at least one basic nitrogen atom.

3. The product of claim 1 wherein the monomeric triamino compound has at least two basic nitrogen atoms.

4. The product of claim 3 wherein the polycarboxy acid is a dicarboxy acid.

5. The product of claim 4 wherein the monomeric triamino compound is diethylene triamino.

6. The product of claim 1 wherein the dicarboxy acid is diglycollic acid.

7. The product of claim 1 wherein the dicarboxy acid is maleic acid.

8. The product of claim 1 wherein the dicarboxy acid is phthalic acid.

9. The product of claim 1 wherein the dicarboxy acid is citraconic acid.

10. The product of claim 1 wherein the dicarboxy acid is succinic acid.

No references cited. 

1. A HYDROPHILE SYNTHETIC PRODUCT WHICH IS THE ESTER OF (A) A POLYCARBOXY ACID SELECTED FROM THE GROUP CONSISTING OF ACYCLIC AND ISOCYCLIC DICARBOXY AND TRICARBOXY ACIDS, COMPOSED OF CARBON, HYDROGEN AND OXYGEN AND HAVING NOT MORE THAN 8 CARBON ATOMS AND (B) A HIGH MOLAL OXYPROPYLATED MONOMERIC ACYLIC TRIAMINO COMPOUND, WITH THE PROVISO THAT THE MONOMERIC TRIAMINO COMPOUND BE FREE FROM ANY RADICAL HAVING AT LEAST 8 UNINTERRUPTED CARBON ATOMS AND BE COMPOSED OF ELEMENTS SELECTED FROM THE GROUP CONSISTING OF CARBON, HYDROGEN, OXYGEN AND NITROGEN, THAT IT HAVE A MOLECULAR WEIGHT OF NOT OVER 800 AND AT LEAST A PLURALITY OF REACTIVE HYDROGEN ATOMS, THAT THE OXYPROPYLATED MONOMERIC TRIAMINO COMPOUND BE WITHIN THE MOLECULAR WEIGHT RANGE OF 2,500 TO 30,000 ON AN AVERAGE STATISTICAL BASIS, THAT THE RATIO OF PROPYLENE OXIDE PER REACTIVE HYDROGEN ATOM OF THE MONOMERIC TRIAMINO COMPOUND BE WITHIN THE RANGE OF 7 TO 70, THAT THE MONOMERIC TRIAMINO COMPOUND NOT REPRESENT MORE THAN 20% BY WEIGHT OF THE OXYPROPYLATED MONOMERIC TRIAMINO COMPOUND ON A STATISTICAL BASIS, THAT THE PRECEDING PROVISOS ARE BASED ON THE ASSUMPTION OF COMPLETE REACTION INVOLVING THE PROPYLENE OXIDE AND THE MONOMERIC TRIAMINO COMPOUND, THAT THE NITROGEN ATOMS BE LINKED BY ETHYLENE GROUPS AND THAT THE RATIO OF (A) TO (B) BE ONE MOLE OF (A) FOR EACH REACTIVE HYDROGEN ATOM PRESENT IN (B). 